Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry Supporting Information

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1 Supporting Information Base free aryl coupling of diazonium compounds and boronic esters: Self activation allowing an overall highly practical process Bonin-Dubarle Hélène, a Delbrayelle Dominique b Demonchaux Patrice b and Gras Emmanuel a,c*! a) CNRS, Université Paul Sabatier; LSPCMIB; 118, route de Narbonne, F Toulouse Cedex 9 b) Minakem, 145, Chemin des Lilas, F Beuvry-La-Forêt, France c) Present Address: CNRS; LCC; 205 route de Narbonne, F Toulouse, France; Université de Toulouse; UPS; INPT; LCC; F31077 Toulouse, France emmanuel.gras@lcc-toulouse.fr 1/ General details... S2 2/ 11B and 19F spectra of mixtures of phenyl pinacol boronic ester and fluoride salt... S3 3/ Typical procedure for the synthesis of aryl dioxazaborocanes... S4 4/ Typical procedure for the synthesis of aryl diazoniums... S9 5/ Typical procedure for cross-coupling... S12 6/ 1 H, 13 C{ 1 H}, 19 F{ 1 H}, 11 B{ 1 H} NMR spectra of dioxazaborocanes... S21 7/ 1 H, 13 C{ 1 H}, 19 F{ 1 H}, 11 B{ 1 H} NMR spectra of diazoniums salts... S33 8/ 1 H, 13 C{ 1 H}, 19 F{ 1 H} (when relevant) spectra of products of cross coupling. S45 S1

2 General details All reactions requiring anhydrous conditions were conducted in a flame-dried apparatus under an atmosphere of argon. THF and diethyl ether were distilled from Na/benzophenone. All other reagents were used as received or when stated were purified according to standard procedures (Armarego, W.L.F.; Chai, C. Purification of Laboratory Chemicals, 5 th edition; 2003; Butterworth-Heinmann Ed.). Petrol ether refers to petroleum fraction boiling between 35 C and 70 C. Chromatography columns were carried out on silica gel (35-70!m). 1 H, 13 C{ 1 H}, 11 B{ 1 H}, 19 F{ 1 H} NMR spectra were recorded with Bruker Advance spectrometers at the specified frequencies. 1 H and 13 C chemical shifts are reported as " values (part per million) relative to TMS and referenced to the internal residual undeuterated solvent. 11 B chemical shifts are reported as " values (part per million) relative to BF 3.Et 2 ; Large patterns appearing on 11 B spectra from approximately -100 to 100 ppm correspond to the background signal of the NMR tube and spectrometer probe. 19 F chemical shifts are reported as " values (part per million) relative to CFCl 3. Coupling constants (J) are given in Hz, multiplicities are given as multiplet (m), singlet (s), doublet (d), triplet (t), quartet (q) or combination of where applicable. Broadness of a signal is stated with its multiplicity (br). Mass spectra were obtained from the Service Commun de Spectrometrie de Masse de la Structure Fédérative Toulousaine en Chimie Moléculaire and recorded on a Thermoquest TSQ 7000 spectrometer. S2

3 11B and 19F spectra of equimolar mixtures of phenyl pinacol boronic ester and fluoride salt With one molar equivalent of KF, the pic at ppm correspond to the free boronate ester; the one appearing at 5.18 ppm correspond to a ate complex (donation of a fluoride anion into the empty orbital of the boron). The ate complex is formed in a greater extent (and/or is more soluble with a Cs + counterion) with one molar equivalent of CsF accounting for an observed better reactivity. S3

4 Typical procedure for the synthesis of aryl dioxazaborocanes (except for 2-fluoro- 3-methoxyphenyldioxazaborocane) To a solution of bromoaryl (1 eq) in THF (2 ml/mmol, distilled) under argon at -78 C is added n-buli (1 eq) at such a rate that the temperature is kept below -78 C. The resulting mixture is stirred for 10 minutes at -78 C. B(iPr) 3 (1 eq) is then added at such a rate that the temperature is kept below -78 C. The resulting white mixture is stirred for one hour while allowed to warm to room temperature. Diethyl ether (20 ml) and NH 4 Cl sat solution (20 ml) are then added, and the resultant mixture is stirred for 30 more minutes. The organic and aqueous phases are separated, the aqueous phase is then extracted with ether (2X20 ml), and the organic phases are washed with brine (2X5 ml). The organic phase is dried over MgS 4 and filtered. The diethanolamine solution (i-prh, 3M, 1 eq) is added and the resulting mixture is stirred for 10 minutes. A solid precipitates instantly. The mixture is filtered, and the solid is washed with ether and dried under vacuum. All the compounds are white solids, with melting points higher than 200 C. Carbons bearing the boron atom are expectedly not detected in 13 C NMR. 4,5,7,8-Tetrahydro-2-(2 -fluoro-3 -methoxyphenyl)-6h-[1,3,6,2]dioxazaborocane This compound was made directly by addition of the 3M diethanolamine solution to the corresponding boronic acid in ether. B NH F 704 mg, 2.95 mmol, 98 % (from the corresponding boronic acid). 1 H NMR (DMS-d 6, 300 MHz), " = 7.08 (s br, 1H), (m, 3H), (td, J = 9.2 Hz, J = 5.4 Hz, 2H), 3.76 (s, 3H), (m, 2H), (tdd, J = 11.7 Hz, J = 9.2 Hz, J = 6.9 Hz, 2H), (m, 2H). 13 C NMR (DMS-d 6, 75.5 MHz), " = (d, 1 J = 238 Hz), (d, 2 J = 14.4 Hz), (d, J = 10.8 Hz), (d, J = 3.6 Hz), (d, J = 1.6 Hz), 62.9, 56.2, B NMR (DMS-d 6, 96.3 MHz), " = F NMR (DMS-d 6, MHz), " = S4

5 MS(DCI-CH 4 ): [MH] +. EA : C = %, H = 6.61 %, N = 5.86 % (calculated for C 11 H 15 BFN 3 : C = %, H = 6.32 %, N = 5.86 %) IR (cm -1 ): 3147 (br), 2959, 2881, 1450, 1438, 1269, 1231, 1067, ,5,7,8-Tetrahydro-2-(phenyl)-6H-[1,3,6,2]dioxazaborocane B NH 2.22 g, 11.6 mmol, 73 %. 1 H NMR (DMS-d 6, 300 MHz), " = (m, 2H), (m, 3H), 6.89 (s br, 1H), (td, J = 9.2 Hz, J = 5.4 Hz, 2H), (m, 2H), (tdd, J = 11.7 Hz, J = 9.0 Hz, J = 6.9 Hz, 2H), (m, 2H). 13 C NMR (DMS-d 6, 75.5 MHz), " = 133.1, 127.2, 126.8, 63.4, B NMR (DMS-d 6, 96.3 MHz), " = MS(DCI-CH 4 ): [MH] +. EA : C = %, H = 7.28 %, N = 7.27 % (calculated for C 10 H 14 BN 2, C = %, H = 7.39 %, N = 7.33 %). IR (cm -1 ): 3118 (br), 2927, 2865, 1458, 1214, 1064, 751, ,5,7,8-Tetrahydro-2-(4 -methoxyphenyl)-6h-[1,3,6,2]dioxazaborocane B NH 2.73 g, 12.4 mmol, 77%. 1 H NMR (DMS-d 6, 300 MHz), " = 7.34 (d, J = 8.5 Hz, 2H), 6.76 (d, J = 8.5 Hz, 2H), (td, J = 9.2 Hz, J = 5.4 Hz, 2H), (m, 2H), 3.70 (s, 3H), (tdd, J = 11.7 Hz, J = 9.0 Hz, J = 6.9 Hz, 2H), (m, 2H). 13 C NMR (DMS-d 6, 75.5 MHz), " = 158.9, 134.2, 112.8, 63.4, 55.2, B NMR (DMS-d 6, 96.3 MHz), " = MS (DCI-NH 3, MeCN) m/z: [M-NH 4 ] +. S5

6 EA : C = %, H = 7.32 %, N = 6.21 % (calculated for C 11 H 16 BN 3, C = %, H = 7.30 %, N = 6.34 %) IR (cm -1 ): 3137 (br), 3031, 2879, 2836, 1600, 1282, 1220, 1174, 1080, 1065, ,5,7,8-Tetrahydro-2-(4 -hydroxyphenyl)-6h-[1,3,6,2]dioxazaborocane 3 equivalents of t-buli were used instead of 1 equivalent of n-buli. H B NH 265 mg, 1.28 mmol, 63%. 1 H NMR (DMS-d 6, 300 MHz), " = 8.85 (s, 1H), 7.22 (d, J = 8.1 Hz, 2H), 6.71 (s, 1H), 6.60 (d, J = 8.1 Hz, 2H), (td, J = 9.2 Hz, J = 5.4 Hz, 2H), (m, 2H), (tdd, J = 11.7 Hz, J = 9.2 Hz, J = 6.9 Hz, 2H), (m, 2H). 13 C NMR (DMS-d 6, 75.5 MHz), " = 156.1, 133.6, 113.7, 62.8, B NMR (DMS-d 6, 96.3 MHz), " = MS(DCI-CH 4 ): [MH] + ; HRMS(DCI-CH 4 ): [MH] + (calculated for C 10 H 15 BN 3 : ). IR (cm -1 ): 3180, 3099 (br), 2960, 28778, 1608, 1583, 1228, 1074, 831, ,5,7,8-Tetrahydro-2-(4 -formylphenyl)-6h-[1,3,6,2]dioxazaborocane The protected 4-bromobenzaldehyde was used for the lithiation. The acidic hydrolysis was done using HCl 2N/NaCl sat before addition of diethanolamine. B NH 2.41 g, 11.0 mmol, 73%. 1 H NMR (DMS-d 6, 300 MHz), " = 9.89 (s, 1H), 7.67 (d, J = 8.1 Hz, 2H), 7.59 (d, J = 8.1 Hz, 2H), 6.96 (s, 1H), (td, J = 9.2 Hz, J = 5.4 Hz, 2H), (m, 2H), (tdd, J = 11.7 Hz, J = 9.0 Hz, J = 6.9 Hz, 2H), (m, 2H). S6

7 13 C NMR (DMS-d 6, 75.5 MHz), " = 193.9, 135.5, 133.7, 128.4, 63.6, B NMR (DMS-d 6, 96.3 MHz), " = MS(DCI-CH 4 ): [MH] + ; HRMS(DCI-CH 4 ): [MH] + (calculated for C 11 H 15 BN 3 : ). IR (cm -1 ): 3137 (br), 2857, 1701, 1598, 1224, 1081, ,5,7,8-Tetrahydro-2-((1,3 -dioxolan-2 -yl)phenyl)-6h-[1,3,6,2]dioxazaborocane B NH 1.31 g, 5.0 mmol, 63 %. 1 H NMR (DMS-d 6, 300 MHz), " = 7.54 (s, 1H), (m, 1H), (m, 2H), 6.92 (s br, 1H), 5.66 (s, 1H), (m, 2H), (m, 2H), (td, J = 9.2 Hz, J = 5.4 Hz, 2H), (m, 2H), (tdd, J = 11.7 Hz, J = 9.2 Hz, J = 6.9 Hz, 2H), (m, 2H). 13 C NMR (DMS-d 6, 75.5 MHz), " = 136.4, 134.0, 131.5, 126.9, 125.3, 104.3, 65.2, 63.5, RMN 11 B (DMS-d 6, 96.3 MHz), " = MS(DCI-CH 4 ): [MH] +. EA : C = %, H = 7.18 %, N = 5.32 % (calculated for C 13 H 18 BN 4 : C = %, H = 6.90 %, N = 5.32 %). IR (cm -1 ): 3090 (br), 2892, 2854, 1431, 1284, 1159, 1071, 983, ,5,7,8-Tetrahydro-2-(3 -formylphenyl)-6h-[1,3,6,2]dioxazaborocane The protected 3-bromobenzaldehyde was used for the lithiation. The acidic hydrolysis was done using HCl 2N/NaCl sat before addition of diethanolamine. S7

8 B NH 1.11 g, 5.0 mmol, 63 %. 1 H NMR (DMS-d 6, 300 MHz), " = 9.99 (s, 1H), 7.99 (t, J = 1.3 Hz, 1H), 7.76 (td, J = 7.4 Hz, J = 1.3 Hz, 1H), 7.70 (td, J = 7.4 Hz, J = 1.3 Hz, 1H), 7.42 (t, J = 7.4 Hz, 1H), 7.01 (s br, 1H), (td, J = 9.2 Hz, J = 5.4 Hz, 2H), (m, 2H), (tdd, J = 11.7 Hz, J = 9.2 Hz, J = 6.9 Hz, 2H), (m, 2H). 13 C NMR (DMS-d 6, 75.5 MHz), " = 194.1, 139.2, 135.0, 134.3, 127.7, 127.5, 63.1, B NMR (DMS-d 6, 96.3 MHz), " = MS(DCI-CH 4 ): [MH] +. EA : C = %, H = 6.60 %, N = 6.26 % (calculated for C 11 H 14 BN H 2 : C = 58.68%, H = 6.57 %, N = 6.22 %). IR (cm -1 ): 3083 (br), 2863, 1692, 1588, 1464, 1284, 1198, 1144, 1067, ,5,7,8-Tetrahydro-2-(4 -cyanophenyl)-6h-[1,3,6,2]dioxazaborocane Lithiation and addition of B(iPr) 3 were performed at -100 C. N B NH 2.44 g, 11.3 mmol, 71%. 1 H NMR (DMS-d 6, 300 MHz), " = 7.61 (s, 4H), (td, J = 9.2 Hz, J = 5.4 Hz, 2H), (m, 2H), (tdd, J = 11.8 Hz, J = 9.2 Hz, J = 6.9 Hz, 2H), (m, 2H). 13 C NMR (DMS-d 6, 75.5 MHz), " = 133.9, 130.7, 120.3, 109.5, 63.4, B NMR (DMS-d 6, 96.3 MHz), " = MS(DCI-CH 4 ): [MH] +. EA : C = %, H = 6.13 %, N = % (calculated for C 11 H 13 BN H 2 : C = %, H = 6.20 %, N = %). IR (cm -1 ): 3138 (br), 3040, 2865, 2218, 1466, 1279, 1236, 1072, 823, 786. S8

9 Typical procedure for the synthesis of aryl diazoniums To a suspension of the aniline (1 eq) in distilled water (0.4 ml/mmol) is added dropwise HBF 4 (50% wt in water, 1.7 eq). The mixture is cooled to 0 C, and the NaN 2 (1 eq) solution in water (saturated solution) is added dropwise. During the addition, the temperature was carefully kept below 5 C, and the resulting mixture was stirred at 0 C for 30 minutes. The resulting precipitate was collected by filtration and dissolved in the minimum amount of acetone. Diethyl ether was added until precipitation of a solid, which is filtered, washed with ether and dried under vacuum. 4-nitrophenyl diazonium tetrafluoroborate 2 N N 2 BF 4 Pale orange solid, 1.97 g, 8.3 mmol, 78 % 1 H NMR (Acetone-d 6, 300 MHz), ": 9.07 (d, J = 9.7 Hz, 2H), 8.75 (d, J = 9.7 Hz, 2H). 13 C NMR : the compound was not stable enough in solution to get the 13 C NMR spectrum. 11 B NMR (Acetone-d 6, 96.3 MHz), ": F NMR (Acetone-d 6, MHz), ": IR (cm -1 ): 3437, 3029, 2308, 1536, 1358, 1318, 1055, 858, 742 Ref : Microchimica Acta 2006, 152, 225 ( 1 H) 4-methoxyphenyl diazonium tetrafluoroborate N 2 BF 4 Pale blue-grey solid, 1.80 g, 8.1 mmol, 75%. 1 H NMR (Acetone-d 6 +DMS-d 6, 300 MHz), ": 8.72 (d, J = 9.3 Hz, 2H), 7.51 (d, J = 9.3 Hz, 2H), 4.13 (s, 3H). 13 C NMR (Acetone-d 6 +DMS-d 6, 75.5 MHz), ": 169.3, 136.2, 117.3, B NMR (DMS-d 6, 96.3 MHz), ": F NMR (DMS-d 6, MHz), ": IR (cm -1 ): 3430, 3115, 2992, 2240, 1583, 1290, 1100, 842. Ref : J. rg. Chem. 2007, 72, 9609 ( 1 H, 13 C), J. rg. Chem. 2008, 73, 316 (IR). S9

10 2-Acetophenyl diazonium tétrafluoroborates N 2 BF 4 Pale orange solid, 706 mg, 5.0 mmol, 50 % 1 H NMR (MeCN-d 3 + Acetone-d 6, 300 MHz), ": 8.86 (dd, J = 8.1 Hz, J = 1.2 Hz, 1H), 8.59 (dd, J = 7.9 Hz, J = 1.2 Hz, 1H), 8.44 (td, J = 7.9 Hz, J = 1.2 Hz, 1H), 8.22 (dd, J = 8.1 Hz, J = 1.2 Hz, 1H), 2.80 (s, 3H). 13 C NMR (MeCN-d 3 + Acetone-d 6, 75.5 MHz), ": 206.4, 141.6, 137.0, 136.2, 135.2, 133.3, B NMR (MeCN-d 3 + Acetone-d 6, 96.3 MHz), ": F NMR (MeCN-d 3 + Acetone-d 6, MHz), ": IR (cm -1 ):3040, 2273, 1697, 1590, 1568, 1265, 1101, 1030, bromophenyl diazonium tetrafluoroborate Br N 2 BF 4 White solid, 1.98 g, 7.3 mmol, 68 % 1 H NMR (Acetone-d 6, 300 MHz), ": 8.76 (d, J = 9.3 Hz, 2H), 8.32 (d, J = 9.3 Hz, 2H). 13 C NMR (DMS-d 6, 75.5 MHz), ": 137.1, 135.0, 134.4, B NMR (Acetone-d 6, 96.3 MHz), ": F NMR (Acetone-d 6, MHz), ": Ref : J. rg. Chem. 2008, 73, 316 (IR), Int. J. Mass. Spectro. 2002, 218, 131 (MS) 4-iodophenyl diazonium tetrafluoroborate I N 2 BF 4 Pale yellow solid, 2.48 g, 7.8 mmol, 72 % S10

11 1 H NMR (DMS-d 6, 300 MHz), ": 8.42 (d, J = 8.4 Hz, 2H), 8.33 (d, J = 8.4 Hz, 2H). 13 C NMR (DMS-d 6, 75.5 MHz), ": 140.8, 133.3, 115.4, B NMR (DMS-d 6, 96.3 MHz), ": F NMR (DMS-d 6, MHz), ": IR (cm -1 ): 3057, 3021, 2258, 1542, 1082, 1030, 824, 524. Ref : Tetrahedron 2006, 62, 2576 ( 1 H). 3-bromophenyl diazonium tetrafluoroborate N 2 BF 4 Br Pale orange solid, 1.97 g, 7.3 mmol, 73 % 1 H NMR (DMS-d 6 + Acetone-d 6, 300 MHz), ": 9.07 (t, J = 2.0 Hz, 1H), 8.84 (ddd, J = 8.3 Hz, J = 2.0 Hz, J = 0.9 Hz, 1H), 8.53 (ddd, J = 8.3 Hz, J = 2.0 Hz, J = 0.9 Hz, 1H), 8.00 (t, J = 8.3 Hz, 1H). 13 C NMR (DMS-d 6 + Acetone-d 6, 75.5 MHz), ": 144.2, 134.7, 133.3, 132.3, 122.7, B NMR (DMS-d 6 + Acetone-d 6, 96.3 MHz), ": F NMR (DMS-d 6 + Acetone-d 6, MHz), ": IR (cm -1 ): 3098, 3033, 2306, 1575, 1464, 1078, 1029, 787, 651. S11

12 Typical procedure for the synthesis of the biaryls by coupling of aryl dioxazaborocanes with aryl diazoniums A solution of diazonium salt (1.2 eq, except nitrobenzene diazonium 1.5 eq), of aryl dioxazaborocane (1 eq) and of Pd/C (0.05 eq) in MeH is heated at 50 C, until the evolution of N 2 has ceased. The mixture is filtered on a Celite bed, which is rinsed with dichloromethane (the diazonium consumption is checked by a colorimetric test with!- naphthol). The solvent is evaporated and the resulting residue is purified by a filtration over silica or by flash chromatography. The solvent is then evaporated. 4 -nitrobiphenyl N 2 Yellow solid, 84 mg, 0.42 mmol, 88%. Chromatography solvent: DCM/EP 50/50 1 H NMR (CDCl 3, 300 MHz), " = 8.29 (d, J = 8.7 Hz, 2H), 7.73 (d, J = 8.7 Hz, 2H), (m, 2H), (m, 3H). 13 C NMR (CDCl 3, 75.5 MHz), " = 147.6, 147.1, 138.8, 129.2, 129.0, 127.8, 127.4, Rf = 0.62 (DCM/EP 50 :50). Ref : rg. Lett., 2004, 6, 4435 ( 1 H, 13 C, Mp, MS, IR, EA) 4-methoxy-4 -nitrobiphenyl N 2 Yellow solid, 95 mg, 0.41 mmol, 83%. Chromatography solvent: Et 2 /EP 10/90 1 H NMR (CDCl 3, 300 MHz), " = 8.24 (d, J = 8.7 Hz, 2H), 7.67 (d, J = 8.7 Hz, 2H), 7.58 (d, J = 8.7 Hz, 2H), 7.02 (d, J = 8.7 Hz, 2H), 3.87 (s, 3H). 13 C NMR (CDCl 3, 75.5 MHz), " = 160.4, 147.1, 146.4, 130.9, 128.5, 127.0, 124.0, 114.5, MS (DCI-CH 4 ): [MH] +, HRMS (DCI-CH 4 ) : [MH] + (calculated for C 13 H 11 N 3 : ). Rf = 0.30 (Et 2 /EP 10 :90). Ref : JACS 1987, 109, 5478 ( 1 H, Mp, IR) S12

13 S13

14 4-formyl-4 -nitrobiphenyl N 2 Pale yellow solid, 105 mg, 0.46 mmol, 92%. Chromatography solvent: DCM 1 H NMR (CDCl 3, 300 MHz), " = (s, 1H), 8.32 (d, J = 9.1 Hz, 2H), 8.00 (d, J = 8.5 Hz, 2H), 7.79 (d, J = 8.8 Hz, 4H). 13 C NMR (CDCl 3, 75.5 MHz), " = 191.7, 147.8, 146.1, 144.5, 136.3, 130.5, 128.3, 128.1, Mp = C. IR (cm -1 ): 3069, 2924, 1701, 1605, 1510, 1344, 819. Rf = 0.67 (DCM) Ref : Tetrahedron 2007, 63, ( 1 H, 13 C, MS) 3-formyl-4 -nitrobiphenyl N 2 Yellow solid, 109 mg, 0.48 mmol, 96%. Chromatography solvent: DCM 1 H NMR (CDCl 3, 300 MHz), " = (s, 1H), 8.30 (d, J = 8.7 Hz, 2H), 8.12 (t, J = 1.7 Hz, 1H), (td, J = 7.5 Hz, J = 1.5 Hz, 1H), (m, 1H), 7.77 (d, J = 8.7 Hz, 2H), 7.67 (t, J = 7.7 Hz). 13 C NMR (CDCl 3, 75.5 MHz), " = 191.7, 147.4, 145.9, 139.6, 137.0, 133.0, 130.2, 129.9, 128.0, 127.9, MS (DCI-CH 4 ): [MH] +, HRMS (DCI-CH 4 ) : [MH] + (calculated for C 13 H 9 N 3 : ). Mp = C. IR (cm -1 ): 3071, 1693, 1597, 1509, 1342, 851, 751. Rf = 0.5 (DCM). Ref : Chem. Commun. 2001, 8, 775. S14

15 4-cyano-4 -nitrobiphenyl N N 2 White solid, 16 mg, 0.07 mmol, 15%. Chromatography solvent: DCM/EP 50/50 1 H NMR (CDCl 3, 300 MHz), " = 8.35 (d, J = 8.7 Hz, 2H), 7.80 (d, J = 8.7 Hz, 2H), (m, 4H). 13 C NMR (CDCl 3, 75.5 MHz), " = 147.9, 145.4, 143.1, 132.9, 128.1, 128.0, 124.3, 118.3, MS (DCI-CH 4 ) : [MH] +, HRMS (DCI-CH 4 ) : [MH] + (calculated for C 13 H 9 N 2 2 : ) Rf = 0.30 (DCM/EP 50 :50). Ref : J. rg. Chem. 2006, 71, 7952 ( 1 H, 13 C, Mp, IR) 4 -methoxybiphenyl Solid, 9 mg, 0.05 mmol, 10%. Chromatography solvent: DCM. 1 H NMR (CDCl 3, 300 MHz), " = (m, 4H), (m, 2H), (m, 1H), 6.99 (d, J = 8.7 Hz, 2H), 3.86 (s, 3H). 13 C NMR (CDCl 3, 75.5 MHz), " = 159.2, 140.9, 133.8, 128.8, 128.2, 126.8, 126.7, Ref : rg. Lett., 2004, 6, 4435 ( 1 H, 13 C, Mp, MS, IR, EA) 4-hydroxy-4 -methoxybiphenyl H Dark red crystals, 49 mg, 0.24 mmol, 49%. Chromatography solvent: DCM then DCM/AcEt 97/3 1 H NMR (CDCl 3, 300 MHz), " = 7.87 (d, J = 8.9 Hz, 2H), 7.82 (d, J = 8.9 Hz, 2H), 7.00 (d, J = 8.9 Hz, 2H), 6.91 (d, J = 8.9 Hz, 2H), 3.88 (s, 3H). S15

16 13 C NMR (CDCl 3, 75.5 MHz), " = 161.7, 157.9, 147.2, 147.0, 124.6, 124.4, 115.8, 114.3, 55.6 (C 5 ). IR (cm -1 ): 3415 (br), 2925, 1597, 1584, 1495, 1235, 843. Rf = 0.33 (DCM/AcEt 97 :3). Ref : Tetrahedron 2007, 63, ( 1 H, 13 C, MS); J. Am. Chem. Soc. 1982, 104, 6393 (Mp) 4-formyl-2 -acetylbiphenyl range solid, 21 mg, 0.10 mmol, 20%. Chromatography solvent: EP/Et 2 50/50 1 H NMR (CDCl 3, 300 MHz), " = (s, 1H), 7.94 (d, J = 8.5 Hz, 2H), 7.63 (ddd, J = 7.4 Hz, J = 1.6 Hz, J = 0.5 Hz, 1H), (m, 4H), (ddd, J = 7.4 Hz, J = 1.6 Hz, J = 0.5 Hz, 1H). 13 C NMR (CDCl 3, 75.5 MHz), " = 203.4, 191.8, 147.3, 140.3, 139.4, 135.5, 131.1, 130.4, 130.0, 129.5, (2C). MS (DCI-CH 4 ): [MH] +, HRMS (DCI-CH 4 ) : [MH] + (calculated for C 15 H 13 2 : ). Mp = C. IR (cm -1 ): 3010, 2925, 1698, 1681, 1605, 834, 776. Rf = 0.40 (EP/Et 2 50 :50). 4 -bromobiphenyl Br Beige solid, 101 mg, 0.43 mmol, 86%. Chromatography solvent : EP 1 H NMR (CDCl 3, 300 MHz), " = (m, 4H), (m, 5H). 13 C NMR (CDCl 3, 75.5 MHz), " = 140.1, 139.9, 131.8, 128.9, 128.7, 127.6, 126.9, Rf = 0.60 (EP). S16

17 Ref : J. rg. Chem. 2006, 71, 244 ( 1 H, 13 C, MS), Tetrahedron 2006, 62, 5603 ( 1 H, MS, Mp, IR) 4-methoxy-4 -bromobiphenyl Br White solid, 105 mg, 0.40 mmol, 80%. Chromatography solvent : Et 2 /EP 10/90 1 H NMR (CDCl 3, 300 MHz), " = 7.53 (d, J = 8.7 Hz, 2H), 7.49 (d, J = 8.7 Hz, 2H), 7.42 (d, J = 8.7 Hz, 2H), 6.98 (d, J = 8.7 Hz, 2H), 3.85 (s, 3H). 13 C NMR (CDCl 3, 75.5 MHz), " = 159.4, 139.8, 132.5, 131.8, 128.3, 128.0, 120.8, 114.4, Rf = 0.50 (Et 2 /EP 10 :90). Ref : J. Fluorine Chem. 2006, 127, 620 ( 1 H, Mp, MS, IR) 4-formyl-4 -bromobiphenyl Br Yellow cristals, 94 mg, 0.36 mmol, 72%. Chromatography solvent: DCM/EP 50/50 1 H NMR (CDCl 3, 300 MHz), " = (s, 1H), 7.94 (d, J = 8.5 Hz, 2H), 7.70 (d, J = 8.5 Hz, 2H), 7.59 (d, J = 8.7 Hz, 2H), 7.48 (d, J = 8.7 Hz, 2H). 13 C NMR (CDCl 3, 75.5 MHz), " = 191.8, 145.9, 138.6, 135.5, 132.2, 130.4, 128.9, 127.5, MS (DCI-CH 4 ) : [MH] +, HRMS (DCI-CH 4 ) : [MH] + (calculated for C 13 H 10 Br: ). IR (cm -1 ): 3047, 2818, 1698, 1603, 812, 497. Rf = 0.28 (DCM/EP 50 :50). Ref : Tetrahedron 2006, 62, 5092 ( 1 H, Mp) S17

18 3-formyl-4 -bromobiphenyl Br range liquid, 102 mg, 0.39 mmol, 78%. Chromatography solvent: DCM 1 H NMR (CDCl 3, 300 MHz), " = (s, 1H), 8.04 (s br, 1H), (m, 1H), (m, 1H), (m, 3H), 7.47 (d, J = 8.7 Hz, 2H). 13 C NMR (CDCl 3, 75.5 MHz), " = 192.0, 140.8, 138.4, 136.9, 132.7, 132.0, 129.6, 129.0, 128.6, 127.6, MS (DCI-CH 4 ): [MH] +, HRMS (DCI-CH 4 ): [MH] + (calculated for C 13 H 10 Br: ). IR (cm -1 ): 3062, 1698, 1586, 1477, 1180, 1008, 830, 790. Rf = 0.75 (DCM). 4 -iodobiphenyl I White solid, 123 mg, 0.44 mmol, 88%. Chromatography solvent : EP 1 H NMR (CDCl 3, 300 MHz), " = 7.80 (d, J = 8.5 Hz, 2H), (m, 2H), (m, 3H), 7.37 (d, J = 8.5 Hz, 2H). 13 C NMR (CDCl 3, 75.5 MHz), " = 140.8, 140.1, 137.9, 129.1, 129.0, 127.8, 127.0, Mp = C. IR (cm -1 ): 3050, 1475, 1389, 998, 827, 755, 688, 465. Rf = 0.55 (EP). Ref : J. rg. Chem. 2006, 71, 244 ( 1 H, 13 C, MS) 4-methoxy-4 -iodobiphenyl I S18

19 Yellowish solid, 127 mg, 0.41 mmol, 82%. Chromatography solvent : Et 2 /EP 10/90 1 H NMR (CDCl 3, 300 MHz), " = 7.73 (d, J = 8.5 Hz, 2H), 7.49 (d, J = 8.7 Hz, 2H), 7.29 (d, J = 8.5 Hz, 2H), 6.98 (d, J = 8.7 Hz, 2H), 3.85 (s, 3H). 13 C NMR (CDCl 3, 75.5 MHz), " = 159.5, 140.4, 137.8, 132.6, 128.6, 128.0, 114.4, 92.2, Mp = C. IR (cm -1 ): 3005, 2962, 2934, 1607, 1521, 1479, 1287, 1253, 1035, 809. Rf = 0.83 (DCM). Ref : Synthesis 2007, 613 ( 1 H, 13 C, MS) 3 -bromobiphenyl Br Yellow liquid, 104 mg, 0.45 mmol, 90%. Chromatography solvent: DCM 1 H NMR (CDCl 3, 300 MHz), " = 7.78 (t, J = 1.8 Hz, 1H), (m, 7H), 7.32 (t, J = 7.8 Hz, 1H). 13 C NMR (CDCl 3, 75.5 MHz), " = 143.4, 139.8, 130.4, 130.3, 130.2, 129.0, 128.0, 127.2, 125.8, MS (DCI-CH 4 ) : [MH] +, HRMS (DCI-CH 4 ) : [MH] + (calculated for C 12 H 10 Br: ). IR (cm -1 ): 3061, 3031, 1591, 1559, 1471, 777, 753, 696. Rf = 0.9 (DCM). Ref : J. rg. Chem. 2006, 71, 1230 ( 1 H, 13 C) 2-fluoro-3-methoxy-3 -bromo-biphenyl F Br range oil, 108 mg, 0.38 mmol, 77 %. Chromatography solvent: DCM S19

20 1 H NMR (CDCl 3, 300 MHz), " = (m, 1H), (m, 2H), 7.31 (td, J = 7.7 Hz, J = 0.4 Hz, 1H), 7.13 (ddd, J = 8.4 Hz, J = 7.7 Hz, J = 1.5 Hz, 1H), (m, 2H). 13 C NMR (CDCl 3, 75.5 MHz), " = (d, J = 248 Hz), (d, J = 11.1 Hz), 137.6, (d, J = 3.0 Hz), 130.6, 129.8, (d, J = 11.1 Hz), (d, J = 3.3 Hz), (d, J = 5.0 Hz), 122.4, (d, J = 2.1 Hz), (d, J = 1.7 Hz), F NMR (CDCl 3, MHz), " = MS (DCI-CH 4 ): [MH] +, HRMS (DCI-CH 4 ) : [MH] + (calculated for C 13 H 11 BrF: ). IR (cm -1 ): 3064, 3007, 2937, 2839, 1582, 1560, 1480, 1461, 1271, 1124, 1031, 772, 729, 692. Rf = 0.93 (DCM). 4-methoxy-3 -bromobiphenyl Br range solid, 105 mg, 0.40 mmol, 80%. Chromatography solvent : Et 2 /EP 10/90 1 H NMR (CDCl 3, 300 MHz), " = 7.75 (t, J = 1.9 Hz, 1H), 7.55 (d, J = 8.9 Hz, 2H), (m, 2H), 7.32 (t, J = 7.7 Hz, 1H), 7.03 (d, J = 8.9 Hz, 2H), 3.90 (s, 3H). 13 C NMR (CDCl 3, 75.5 MHz), " = 159.6, 143.0, 132.2, 130.3, 129.8, 129.6, 128.2, 125.3, 122.9, 114.4, MS (DCI-CH 4 ): [MH] +, HRMS (DCI-CH 4 ): [MH] + (calculated for C 13 H 12 Br: ). Mp = C. IR (cm -1 ): 3038, 2955, 2837, 1607, 1516, 1472, 1252, 1019, 836, 788. Rf = 0.83 (DCM). S20

21 3-formyl-3 -bromobiphenyl Br Yellow oily solid, 103 mg, 0.40 mmol, 80%. Chromatography solvent: DCM 1 H NMR (CDCl 3, 300 MHz), " = (s, 1H), 8.04 (s br, 1H), (m, 1H), (m, 1H), 7.74 (t, J = 1.9 Hz, 1H), 7.60 (t, J = 7.7 Hz, 1H), (m, 2H), 7.32 (t, J = 7.7 Hz, 1H). 13 C NMR (CDCl 3, 75.5 MHz), " = 192.2, 141.8, 140.6, 137.0, 133.0, 131.0, 130.6, 130.2, 129.7, 129.3, 128.0, 125.8, MS (DCI-CH 4 ): [MH] +, HRMS (DCI-CH 4 ): [MH] + (calculated for C 13 H 10 Br: ). Mp = IR (cm -1 ): 3061, 2825, 2725, 1699, 1584, 1466, 1288, 1180, 880, 776, 689. Rf = 0.7 (DCM). 4-Methoxy-2 -bromobiphenyl Br Yellowish oil, 509 mg, 1,93 mmol, 43%. Chromatography solvent: EP/DCM gradient from 100/0 to 50/50 1 H NMR (CDCl 3, 400 MHz), " = 7.70 (d, J = 8.0 Hz, 1H), (m, 4H), 7.21 (ddd, J = 8.01 Hz, J = 6,4 Hz, J = 2,8 Hz, 1H), 7.01 (d, J = 8.8 Hz, 2H), 3.90 (s, 3H). 13 C NMR (CDCl 3, 100 MHz), " = 159.1, 142.3, 133.6, 133.2, 131.4, 130.6, 128.5, 127.4, 123.0, 113.4, MS (DCI-CH 4 ): 263 [MH] +, HRMS (DCI-CH 4 ) : [MH] ). Rf = 0.25 (EP/DCM 90:10). (calculated for C 13 H 12 Br: S21

22 4-Methoxy-2 -trifluoromethylbiphenyl F 3 C Clear brown oil, 352 mg, 1,40 mmol, 58%. Chromatography solvent: EP/DCM gradient from 100/0 to 50/50 1 H NMR (CDCl 3, 300 MHz), " = 7.78 (d, J = 7.5 Hz, 1H), 7.58 (dd, J = 7.5Hz, J = 7.5 Hz, 1H), 7.48 (dd, J = 7.5Hz, J = 7.5 Hz, 1H), 7,37 (d, J = 7.5 Hz, 1H), 7.31 (d, J = 8.4 Hz, 2H), 6.99 (d, J = 8.4 Hz, 2H), 3.89 (s, 3H). 13 C NMR (CDCl 3, 100 MHz), " = 159.2, (q, J = 1.8 Hz), 132.3, 132.2, 131.3, (q, J = 1.5 Hz), (q, J = 29.6 Hz), 127.1, (q, J = 5.4 Hz), (q, J = Hz), 113.2, F NMR (CDCl 3, MHz), " = MS (DCI-CH 4 ): 253 [MH] +, HRMS (DCI-CH 4 ) : [MH] + (calculated for C 14 H 12 F 3 : ). Rf = 0.10 (Cyclohexane 100%). S22

23 1 H, 13 C, 11 B, 19 F (when relevant) NMR spectra of dioxazaborocanes S23

24 S24

25 4,5,7,8-Tetrahydro-2-(phenyl)-6H-[1,3,6,2]dioxazaborocane S25

26 4,5,7,8-Tetrahydro-2-(4 -methoxyphenyl)-6h-[1,3,6,2]dioxazaborocane S26

27 S27

28 4,5,7,8-Tetrahydro-2-(4 -hydroxyphenyl)-6h-[1,3,6,2]dioxazaborocane S28

29 4,5,7,8-Tetrahydro-2-(4 -formylphenyl)-6h-[1,3,6,2]dioxazaborocane S29

30 S30

31 4,5,7,8-Tetrahydro-2-((1,3 -dioxolan-2 -yl)phenyl)-6h-[1,3,6,2]dioxazaborocane S31

32 4,5,7,8-Tetrahydro-2-(3 -formylphenyl)-6h-[1,3,6,2]dioxazaborocane S32

33 S33

34 4,5,7,8-Tetrahydro-2-(4 -cyanophenyl)-6h-[1,3,6,2]dioxazaborocane S34

35 1 H, 13 C, 19 F, 11 B NMR spectra of diazoniums salts 4-nitrophenyl diazonium tetrafluoroborate S35

36 No 13 C due to compound unstability. S36

37 4-methoxyphenyl diazonium tetrafluoroborate S37

38 S38

39 2-Acetophenyl diazonium tétrafluoroborates S39

40 S40

41 4-bromophenyl diazonium tetrafluoroborate S41

42 S42

43 4-iodophenyl diazonium tetrafluoroborate S43

44 S44

45 3-bromophenyl diazonium tetrafluoroborate S45

46 S46

47 4 -nitrobiphenyl 1 H, 13 C, 19 F (when relevant) spectra of products of cross coupling S47

48 4-methoxy-4 -nitrobiphenyl S48

49 4-formyl-4 -nitrobiphenyl S49

50 3-formyl-4 -nitrobiphenyl S50

51 4-cyano-4 -nitrobiphenyl S51

52 4 -methoxybiphenyl S52

53 4-hydroxy-4 -methoxybiphenyl S53

54 4-formyl-2 -acetylbiphenyl S54

55 4 -bromobiphenyl S55

56 4-methoxy-4 -bromobiphenyl S56

57 4-formyl-4 -bromobiphenyl S57

58 3-formyl-4 -bromobiphenyl S58

59 4 -iodobiphenyl S59

60 4-methoxy-4 -iodobiphenyl S60

61 3 -bromobiphenyl S61

62 2-fluoro-3-methoxy-3 -bromo-biphenyl S62

63 S63

64 4-methoxy-3 -bromobiphenyl S64

65 3-formyl-3 -bromobiphenyl S65

66 4-Methoxy-2 -bromobiphenyl S66

67 4-Methoxy-2 -trifluoromethylbiphenyl S67

68 S68